CN102822124B - Method for making a catalyst comprising a phosphorus modified zeolite to be used in a MTO process - Google Patents

Method for making a catalyst comprising a phosphorus modified zeolite to be used in a MTO process Download PDF

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CN102822124B
CN102822124B CN201180015677.7A CN201180015677A CN102822124B CN 102822124 B CN102822124 B CN 102822124B CN 201180015677 A CN201180015677 A CN 201180015677A CN 102822124 B CN102822124 B CN 102822124B
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zeolite
catalyzer
phosphorus
technique
weight
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CN102822124A (en
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N.内斯特伦科
S.范唐克
D.米诺克斯
J-P.达思
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Total Petrochemicals Research Feluy SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)

Abstract

The present invention is the use of a catalyst in a MTO process to convert an alcohol or an ether into light olefins, wherein said catalyst comprises a phosphorus modified zeolite and is made by a method comprising the following steps in this order, a) the essential portion of the phosphorus is introduced into a zeolite comprising at least one ten members ring in the structure, b) the phosphorus modified zeolite of step a) is mixed with at least a component selected among one or more binders, salts of alkali-earth metals, salts of rare-earth metals, clays and shaping additives, b)* making a catalyst body from mixture b), c) an optional drying step or an optional drying step followed by a washing step, d) a calcination step, d*) an optional washing step followed by drying, e) optionally a small portion of phosphorus is introduced in the course of step b) or b)* or at end of step b) or b)*.

Description

Manufacture the method comprising the catalyzer of phosphorus-modified zeolite being used for MTO technique
Technical field
The present invention relates to the method comprising the catalyzer of phosphorus-modified zeolite for the manufacture of using in MTO technique.More precisely, it relates to the purposes that alcohol or ether are changed into light olefin by catalyzer in MTO technique, and wherein said catalyzer comprises phosphorus-modified zeolite.Alkene is produced by catalytic cracking or Steam cracking processes by petroleum traditionally.These process (particularly steam cracking) by hydrocarbons raw material production light olefin, such as ethene and/or propylene.Ethene and propylene are important large (commodity) petroleum chemicals useful in the kinds of processes for the manufacture of plastics and other compound.
The limited supply of crude oil and the price day by day raised have impelled the alternative techniques found and produce hydrocarbon product.MTO technique produces light olefin if ethene and propylene and heavy hydrocarbon are as butylene.Described MTO technique is conversion methyl alcohol or dme undertaken by contacting with molecular sieve.To the interest of methanol to olefins (MTO) technique based on the following fact: methyl alcohol by coal or Sweet natural gas by producing synthetic gas, then can be processed described synthetic gas and obtaining with methanol.
Background technology
The catalyzer comprising phosphorus-modified zeolite (described phosphorus-modified zeolite is also referred to as P-zeolite) is known.Below prior art describes the various manufacture method of described catalyzer.
US 2,006 106270 relates to difunctional (sense, function) catalyst body ties up to oxygenate (oxygenate) and is converted into purposes in the hydrocarbon synthesis reaction district of the technique of propylene (OTP), and the technique that wherein said oxygenate is converted into propylene (OTP) preferably uses steam diluent run and use moving-burden bed reactor technology in relatively high temperature.Described bifunctional catalyst system comprises the molecular sieve with difunctional performance being scattered in and comprising in the P Modification alumina host of active phosphorus and/or aluminium negatively charged ion.According to explanation, the hydrothermally stable observed when utilizing this P Modification alumina host turns into being moved by phosphorus and/or aluminium negatively charged ion from this matrix or be distributed to combined molecular sieve to cause.These negatively charged ion then can be used for resisting by be exposed to temperature to destroy with the framework of molecular sieve that steam corresponding with the temperature that uses in breeding blanket in OTP reaction zone causes or change the well-known dealumination mechanism of (modification) and repair, malleableize (anneal) and/or molecular sieves stabilized skeleton.
US 4,356,338 discloses and reduces catalyzer coking and the method extending available catalyst life by carrying out pre-treatment with steam and/or P contained compound to catalyzer.Pre-treatment is by following realization: with P contained compound impregnated catalyst or catalyzer/binding agent combination, with deposit thereon weight based on processed catalyzer or catalyzer/binder matrix about 4 % by weight phosphorus, and preferably about 2 % by weight-15 % by weight phosphorus.
US 5,231,064 relate to comprise clay and zeolite fluid catalyst (at least one of described clay and zeolite used P contained compound as primary ammonium phosphate or phosphoric acid process and its at low pH (preferably lower than about 3) spraying dry).Described catalyzer is considered to the wearing and tearing advantageously showing reduction.
EP 511013 A2 provides the improving technique being produced C2-C5 alkene by the alkene of higher alkene or paraffinic feed or mixing and paraffinic feed.According to the prior art, described hydrocarbon feed is contacted, to produce light alkene under the temperature raised, high space velocity and low hydrocarbon partial pressure with specific ZSM-5 catalyzer.Described catalyzer uses steam treatment before transforming for hydrocarbon.Active catalyst component is the phosphorous ZSM-5 of the surperficial Si/Al ratio had within the scope of 20-60.Preferably, add phosphorus by following to formed ZSM-5: according to such as at United States Patent (USP) 3,972, the program described in 832, floods ZSM-5 with phosphorus compound.Not too preferably, described phosphorus compound can be added into and be formed in the multicomponent mixture of catalyzer by it.Described phosphorus compound adds to be enough to provide the amount with 0.1-10 % by weight, the preferably final ZSM-5 composition of 1-3 % by weight phosphorus.
By described phosphorous ZSM-5 preferably with known binding agent or matrix as combinations such as silicon-dioxide, kaolin, calcium bentonite, aluminum oxide and silico-aluminates (silica aluminate).Described ZSM-5 accounts for 1-50 % by weight, preferably 5-30 % by weight and the most preferably 10-25 % by weight of catalyst composition usually.
EP 568913 A2 describes the method that preparation is suitable for the catalyzer based on ZSM-5 used in the catalyzed conversion of light olefin at methyl alcohol or dme, and wherein it comprises following sequential step:
● the catalyzer based on zeolite ZSM-5 is mixed with silicon dioxide gel and ammonium nitrate solution,
● described mixture is mediated, shaping, dry and calcining,
● this modified zeolite is exchanged with HCl solution at 70-90 DEG C,
● drying also calcines this H-modified zeolite,
● under a reduced pressure with this H-modified zeolite of phosphate impregnation,
● drying also calcines this P-modified zeolite,
● use this P-modified zeolite of solution impregnation of rare earth element under a reduced pressure,
● drying also calcines this P-rare earth-modified zeolite,
● with water vapor, hydrothermal treatment consists is carried out to this P-rare earth-modified zeolite at 500-600 DEG C, and
● calcine this modified zeolite.
WO 03 020667 relates to the technique of being produced alkene particularly ethene and propylene by oxygenate charging, comprise the zeolite catalyst making oxygenate charging different with at least two kinds and contact to form compositions of olefines, wherein the first zeolite catalyst comprises ZSM-5 molecular sieve and the second zeolite catalyst comprises the zeolite molecular sieve being selected from ZSM-22, ZSM-23, ZSM-35, ZSM-48 and composition thereof.Described ZSM-5 can be that unmodified, P Modification, steam are modified as 50% or its various mixture that micro pore volume is reduced to the micro pore volume being no less than non-decatize ZSM-5.According to an embodiment, the modification of described zeolite P contained compound is with the decline of control punch volume.Alternatively, decatize is carried out to zeolite, and before or after decatize, add described phosphorus compound.Amount based on the phosphorus of elements are contained is 0.05 % by weight-20 % by weight and preferably 1 % by weight-10 % by weight, based on the weight of zeolite molecular sieve.Preferably, the atomic ratio of phosphorus to framework aluminum (namely in zeolite framework) is not more than 4:1 and more preferably 2:1-4:1.According to an embodiment, it is by making independent zeolite molecular sieve or contacting with the solution of suitable phosphorus compound with the zeolite that binding agent combines and realize that P Modification agent is attached in the catalyzer of this invention.Solid zeolite or zeolite catalyst are separated from described phosphorus solution, drying is also calcined.In some cases, the phosphorus of interpolation changes into its oxide form in such a situa-tion.Usually the time of 15 minutes to 20 hours is carried out the temperature of 25 DEG C-125 DEG C with the contact of P contained compound.In zeolite, the concentration of phosphorus can be 0.01 % by weight-30 % by weight.The prior art discloses the P-ZSM-5 of non-preparation.
Produce zeolite (as zeolite+binding agent) the P-compound dipping that the usual method comprising the catalyzer of the P-zeolite of preparation is to have prepared in advance, or phosphorus is added in reaction medium.
Patent discloses the scheme being prepared active phase (the phosphatization zeolite of non-preparation) by zeolite phosphatization in a large number, and their purposes in methanol conversion.Some in these reference comprise option blended further with binding agent for described activity.But activity itself is good mutually in the reaction.Assuming that binding agent only plays the effect (situation is usually really not so) of thinner.Owing to relating to the catalyzer of preparation preparation and implementing phosphating step in the first stage, technique of the present invention is different from many preparations of the active phase based on P-zeolite be known in the art.In addition, the phosphatization (formation of active phase) of zeolite not necessarily causes suitable catalyzer in a first step.On the contrary, overall plan causes good catalyzer.
The catalyzer related in the present invention comprises the component that zeolite and at least one are selected from one or more binding agents, alkaline earth salt, rare earth metal salt, clay and shaping additive.Described metal-salt, binding agent and clay be adsorbable phosphorus also, thus interference zeolite, even compete with zeolite, hinder appropriate (proper) zeolite phosphatization.The existence of the trace-metal of Preferential adsorption phosphorus can disturb zeolite phosphatization even more.This usually causes nonselective catalyzer due to poor reproducibility and binding agent hole plug.The inventive process provides the scheme making zeolite optionally phosphatization, which overcome the side effect that binding agent, metal-salt or clay exist.Therefore, the preparation that the invention discloses catalyzer needs to make zeolite phosphatization before introducing other component any is as binding agent, metal, clay and shaping additive.This method guarantees that the reproducibility of preparation, hydrothermal stability and good catalyst performance.
Summary of the invention
The present invention relates to the purposes that alcohol or ether are changed into light olefin by catalyzer in MTO technique, wherein said catalyzer comprises phosphorus-modified zeolite, and the method manufacture by comprising the following steps with this order,
A) phosphorus of major portion (essential portion) be introduced into comprise in the zeolite of at least one ten-ring in the structure,
B) step phosphorus-modified zeolite a) is mixed with at least one component being selected from one or more binding agents, alkaline earth salt, rare earth metal salt, clay and shaping additive,
B) * is by mixture b) manufacture catalyzer body (main body, body),
C) optional drying step or optional drying step and washing step subsequently,
D) calcining step,
D*) optional washing step and drying subsequently,
E) optionally, in step b) or b) during * or in step b) or b) introduce the phosphorus of small portion at the end of *.
Advantageously, zeolite (or molecular sieve) comprise be less than 1000wppm sodium, be less than the potassium of 1000wppm and be less than the iron of 1000wppm.
Advantageously, zeolite comprises the alkali and alkaline earth metal ions being less than 200ppm.
Advantageously, body (bulk) the Si/Al ratio of original zeolitic is lower than 20.Advantageously, zeolite comprise be less than 100ppm redox (red-ox) and noble element as Zn, Cr, Ti, Rh, Mn, Ni, V, Mo, Co, Cu, Cd, Pt, Pd, Ir, Ru, Re.
Phosphorus source is advantageously substantially free of metallic compound.It is advantageously selected from H 3pO 4, ammonium phosphoric acid salt or organic P-compound.
In one embodiment, step e) phosphorus can be used as binder component or clay composition and introduce.
Step a) in the amount of phosphorus that is introduced in zeolite can be 0.5-30 % by weight, but be preferably 0.5-9%.
Advantageously, step a) in, by providing excessive phosphorization agent, P/Al mol ratio is higher than 1.
Preparation steps b) and c) by spraying dry, extrude, oil droplet etc. carries out.
According to the present invention, in step c) and d*) in, be advantageously the time of 0.5-48 hour, the preferably time of about 1-36 hour and most preferably from about time of 2-24 hour by catalyzer with water process.Water is about 10 DEG C-180 DEG C, preferably about 15 DEG C-100 DEG C and the most preferably from about temperature of 20 DEG C-60 DEG C.After water treatment, by catalyzer in about 60-350 DEG C drying.Optionally, water can comprise ammonium or/and be selected from Li, Ag, Mg, Ca, Sr, Ba, Ce, Al, La, and composition thereof at least one of ion.
At the end of step a), it is not enforceable for being separated from reaction medium by P-zeolite, binding agent, alkaline earth salt, rare earth metal salt, clay and shaping additive can be added directly in reaction medium.
In a preferred embodiment, binding agent and the clay of low sodium content is used.
Before step phosphatization a), zeolite can experience various process, comprises ion-exchange, decatize, acid treatment, carries out surface passivation etc. by silica deposit.
In a preferred embodiment, the sodium content in binding agent and clay is less than 5000ppm sodium.
Preferably zeolite structuredly be selected from MFI, MTT, FER, MEL, TON, MWW, EUO, MFS, ZSM-48.
Embodiment
About MTO technique alcohol or ether being changed into light olefin, this technique is described in many patent applications.WO 2004/016572, WO 2005/016856, WO 2008/110526, WO 2008/110528, WO 2008/110530, WO 2009/016153, WO 2009/156434 and WO 2009/016154 can be enumerated, its content is combined in this application.
About the zeolite comprising at least one 10 ring in the structure, crystalline silicate can be enumerated.It is such as by silicon, aluminium, MFI (the ZSM-5 of oxygen and optional boron composition, Silicalite-1, borosilicate zeolite (boralite) C, TS-1), MEL (ZSM-11, silicone zeolite-2, borosilicate zeolite D, TS-2, SSZ-46), FER (ferrierite (Ferrierite), FU-9, ZSM-35), MTT (ZSM-23), MWW (MCM-22, PSH-3, ITQ-1, MCM-49), TON (ZSM-22, Theta-1, NU-10), EUO (ZSM-50, EU-1), the poromerics of MFS (ZSM-57) and ZSM-48 series.
Three letter designations " MFI " and " MEL " represent as by the determined specific crystalline silicate structure type of the structure council of International Zeolite Association separately.The example of MFI type crystalline silicate is synthetic zeolite ZSM-5 and silicone zeolite and other MFI type crystalline silicate as known in the art.The example of the crystalline silicate of MEL series is zeolite ZSM-11 and other MEL type crystalline silicate as known in the art.Other example is borosilicate zeolite D described by International Zeolite Association (Atlas of zeolite structure types, 1987, Butterworths) and silicone zeolite-2.Preferred crystalline silicate has the hole or passage that are limited by ten oxygen rings.
Crystalline silicate is the XO based on being connected to each other by cationic sharing 4the microporous crystalline inorganic polymer of tetrahedral skeleton, wherein X can be trivalent (as Al, B ...) or tetravalence (as Ge, Si ...).The crystalline structure of crystalline silicate is limited by so specific order (order, order): the network of tetrahedron element links together with described specific order.The size of crystalline silicate hole opening is determined by the cationic character existed in the quantity of the tetrahedron element formed needed for hole or Sauerstoffatom and described hole.They have the unique combination of following character: high internal surface area; There is the uniform bore of one or more discrete size; Can ion exchangeable; Good thermostability; With the ability of adsorb organic compounds.Due to the size in the hole of these crystalline silicates and many organic molecules of practical study similar, their control the turnover of reactant and product, cause specific selectivity in catalyzed reaction.The crystalline silicate with MFI structure has the bidirectional crossed pore system having following bore dia: the straight channel along [010]: 0.53-0.56nm and the sinusoidal channel along [100]: 0.51-0.55nm.The crystalline silicate with MEL structure has bidirectional crossed straight hole system, wherein has the bore dia of 0.53-0.54nm along the straight channel of [100].
In a specific embodiment, before phosphatization, decatize is carried out to crystalline silicate, to remove aluminium from crystalline silicate framework.Carry out under the water partial pressure of steam treatment at the temperature of preferred rising within the scope of 425-870 DEG C, more preferably within the scope of 540-815 DEG C with under 1-5 clings to absolute pressure with at 13-200kPa.Preferably, steam treatment is carried out in the atmosphere comprising 5-100% steam.Described steam atmosphere preferably comprises 5-100 volume % steam and 0-95 volume % rare gas element (preferred nitrogen).Preferred atmosphere comprises 72 volume % steam and 28 volume % nitrogen, and namely under 1 atmospheric pressure, steam is 72kPa.Steam treatment preferably implements 1-200 hour, more preferably 20 hours-100 hours.As mentioned above, steam treatment is tending towards the amount reducing the tetrahedral aluminium in crystalline silicate framework by forming aluminum oxide.
In addition, if during the preparation of zeolite treating phosphatization, employed basic metal or alkaline-earth metal, then molecular sieve can be made to experience ion-exchange step.Routinely, ion-exchange uses ammonium salt or mineral acid to carry out in aqueous.
About P to the introducing in zeolite, such as, the manufacture technics of described P-modified zeolite by comprising the steps in the following order:
-introduce P;
If-there is liquid, then by solid and liquid separation;
-optional washing step, or optional drying step, or optional drying step and washing step subsequently;
-calcining step;
Optionally, carry out with the contact of the P contained compound temperature at 40 DEG C-110 DEG C.P by any-mode or such as according to US 3,911, in 041 describe scheme introduce.
Liquid filters advantageous by the temperature at 0-90 DEG C with being separated of solid, centrifugal by the temperature at 0-90 DEG C, by evaporate or equivalent way is carried out.
Optionally, zeolite can be washed after releasing before dry.Advantageously, described drying advantageously carries out 1-10 hour at the temperature of 40-600 DEG C.This drying can be carried out in a stationary situation or in the gas flow.Air, nitrogen or any rare gas element can be used.
Washing step can use a part of cold water (<40 DEG C) or hot water (>40 but <90 DEG C) to carry out in filtration (separating step) period, or solid can be made to experience the aqueous solution (1kg solid/4 aqueous solution) and under reflux conditions process 0.5-10h, evaporation subsequently or filtration.
According to a specific embodiments, the manufacture technics phosphorus-modified zeolite by comprising the steps in the following order:
-select zeolite;
-be the temperature decatize 0.01-200h of 400-870 DEG C in scope;
-optionally, effectively removing lixiviate (leach) the condition of signal portion Al from zeolite with aqueous acid;
-with containing P source the aqueous solution effectively introduce advantageously at least 0.05 % by weight P condition under introduce P;
-by solid and liquid separation;
-optional washing step, or optional drying step, or optional drying step and washing step subsequently;
-optional calcining step.
In steaming step, temperature is preferably 420-870 DEG C, more preferably 480-760 DEG C.Pressure is preferably normal atmosphere and water partial pressure can scope be 13-100kPa.Steam atmosphere preferably comprises 5-100 volume % steam and 0-95 volume % rare gas element (preferred nitrogen).Steam treatment preferably implements 0.01-200 hour, advantageously 0.05-200 hour, more preferably 0.05-50 hour.Steam treatment is tending towards the amount reducing tetrahedral aluminium in crystalline silicate framework by forming aluminum oxide.
Lixiviate can use organic acids as citric acid, formic acid, oxalic acid, tartrate, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, toxilic acid, phthalic acid, m-phthalic acid, fumaric acid, complexon I, HEDTA, ethylenediamine tetraacetic acid (EDTA), trichoroacetic acid(TCA), trifluoroacetic acid or the salt (as sodium salt) of acid or the mixture of the acid two or more or salt carry out.Other mineral acid can comprise mineral acid such as nitric acid, hydrochloric acid, methanesulphonic acid, phosphoric acid, phosphonic acids, sulfuric acid or the salt (as sodium salt or ammonium salt) of such acid or the mixture of the acid two or more or salt.
Residual P content is regulated by P concentration, drying conditions and the washing procedure (if there are the words of washing procedure) comprised in the aqueous acid in P source.Drying step can be imagined between filtration and washing step.
About step b), and binding agent, it is chosen to for using the temperature adopted in the technique of this catalyzer to have tolerance with other condition.Described binding agent is selected from silicon-dioxide, metal silicate, metal oxide as ZrO 2and/or metal or comprise the inorganic materials of gel of mixture of silicon-dioxide and metal oxide.The catalyzer with good shatter strength is provided to be expect.This is because in business uses, expect to prevent the powdered material of catalyst breakage.Such adhesive oxides is usually only for improving the shatter strength of catalyzer.Particularly preferred binding agent for catalyzer of the present invention comprises silicon-dioxide.The relative proportion of fine-grannular crystalline silicate material and binding agent inorganic oxide matrix can vary widely.
About step b) *, except enhancing catalyst strength character, substrate material also allows molecular sieve microcrystal powder to be combined into the larger particle size being suitable for commercial catalyst technique.Can by mixture b) formula be formed as various shape, comprise extrudate, ball and pellet (pill) etc.Binder material usually transforms for the expectation promoting methyl alcohol to light olefin and can be effective or be not effective being porous in nature to a certain extent.Substrate material also can promote the conversion of feed stream and usually provide the selectivity to expectation product reduced relative to catalyzer.
Type for the formation of the silicon dioxide gel of the combined catalyst used in MTO technique is as the organosol of the colloidal silica particles comprising dispersion or the commercially available acquisition of the water-sol.Such as, water glass can be used as silicon dioxide gel.In addition, silica gel, pyrolysis (fumed) or pyrogene (pyrogenic) silicon-dioxide also can be used to provide the silica binder in molecular sieve catalyst.Silicic acid is another kind of possible silica source.If magnesium oxide binding agent expects, then initial slurry will comprise the alkoxyl magnesium through being hydrolyzed.When using zirconia binder to be used for catalyst preparing, preferred starting acidic sol is aqueous zirconium acetate solution, and it preferably combines with urea jelling agent.
About clay, preferably, optionally clay is added in catalyzer.Clay was added in catalyst slurry usually before mixing with molecular sieve and binding agent, and the slurry mixing also spraying dry that will obtain.For including but not limited to kaolin, kaolinite, polynite, saponite, wilkinite, attapulgite and halloysite with the clay forming hardened product in this technique.The binding agent of clay image intensifying granules of catalyst wearability equally contributes intensity, and contributes pellet hardness with the clay that binding agent combines.Clay also starts with short grained form and has higher density, and making provides finer and close particle when combining with molecular sieve and binding agent, thus gives the desired characteristic of higher density.
About alkaline earth salt, rare earth metal salt, metal is Ca, Mg, Sr, Ce, La or its combination advantageously.
About the ratio of P-zeolite, one or more binding agents described, alkaline earth salt, rare earth metal salt, clay and shaping additive, advantageously, the ratio of P-zeolite is the 5-95 % by weight of catalyzer.Catalyzer comprises P-zeolite and is selected from least one component of one or more binding agents, alkaline earth salt, rare earth metal salt, clay and shaping additive.The amount of the P-modified zeolite comprised in catalyzer is more advantageously the 15-90 % by weight of whole catalyzer, the 20-70 % by weight of preferred catalyst.When adding clay, clay forms the about 10-about 80 % by weight of the catalyst product of drying.The concentration of alkaline earth salt and rare earth metal salt can be the 0.1-15 % by weight of catalyzer in metal (Me).Advantageously, in catalyzer, the mol ratio of (Al+Me)/P is within the scope of 0.5-3, and wherein Me is alkaline earth or rare earth.
When P-zeolite is mixed with at least one component being selected from one or more binding agents, alkaline earth salt, rare earth metal salt and clay, catalyst preparation can be become pill (particle, pellet), be extruded into other shape or be formed as ball or spray-dried powders.Typically, all the components is mixed by hybrid technique.Such as, in such technique, by the binding agent of gel form as silicon-dioxide mixes with P-zeolite, and the mixture obtained is extruded into the shape of expectation, as cylindrical or multi-leaf-shaped rod.Spherical form can be made in rotary pelleting machine or by oil dropping technique.Bead is made further by carrying out spraying dry to catalyst suspension.
After this, by catalyzer in air or rare gas element, typically at the temperature calcination 1-48 hour of 350-900 DEG C.Optionally, described air or rare gas element can comprise the steam of 10-90 volume % concentration.
About step c) and d*), the shaping catalyst particle of drying or calcining is optionally by making them contact with the water coke slurry solution of water or ionic compound and arrange (finish).The feature of described water coke slurry solution is, it can occupy the less desirable metallic cation in the ion-exchange site (site) of molecular sieve for removing and/or the metallic cation of introducing expectation is effective.Described less desirable metallic cation is Na, K, Fe, Zn, Cr, Mn, Ni, V, Mo, Co, Cu, Cd.These materials can be derived from the inorganic template material existed in molecular sieve, or more commonly, come from inorganic oxide binder source material (as Alumina gel).Designed by described catalyzer for operation use (processing service) (such as, methyl alcohol is to conversion of olefines) in, these metallic cations can promote side reaction, the speed of reaction slowing down expectation or the catalysis making expected response complicated.Some sources of inorganic oxide binder are substantially free of less desirable metallic cation, and the dried particles therefore using such source to produce not necessarily needs to contact with exchange solution.Washing before and after described arrangement step can be expectation, to fall less desirable solid and/or residual exchange solution from catalyst flush.
According to the present invention, in step c) and d*), advantageously for the time of 0.5-48 hour, preferably about 1-about 36 hours and most preferably from about time of 2-24 hour by catalyzer with water process.Water is about 10 DEG C-180 DEG C, preferably about 15 DEG C-100 DEG C and the most preferably from about temperature of 20 DEG C-60 DEG C.After water treatment, by catalyzer in about 60-350 DEG C drying.Optionally, described water can comprise ammonium or be selected from Li, Ag, Mg, Ca, Sr, Ba, Ce, Al, La, and composition thereof at least one of metallic cation, they do not promote side reaction and make zeolite resist steam dealuminzation and stabilization.
Embodiment
Embodiment 1
By H-type zeolite ZSM-5 (Si/Al=12) sample (comprise 445ppm Na, be less than K, 178ppm Fe, 17ppm Ca of 25ppm and synthesize when not having template) at 550 DEG C under atmospheric pressure at 100%H 2decatize 6h in O.Below this sample is denoted as sample A.
Make the H of solid A and the 3.14M through decatize 3pO 4solution (4.2ml/1g zeolite) under reflux conditions contacts 4h.Then, at room temperature by filtering solid from liquid phase separation from solution.By the material that obtains at 200 DEG C of dry 16h.Below this sample is denoted as sample B.
Make 100g through the H of solid A and the 31g85 % by weight of decatize 3pO 4at 400ml H 2under reflux conditions 4h is contacted in O.Then cool described solution, and 10g xonotlite (Calucium Silicate powder) is added in this mixture, evaporate stirring at room temperature 30 minutes subsequently.Below this sample is denoted as sample C.
Make 100g through the H of solid A and the 109.1g 85 % by weight of decatize 3pO 4at 320ml H 2under reflux conditions 4h is contacted in O.Then 100g xonotlite (Calucium Silicate powder) is added in this mixture, at room temperature stirs 30 minutes subsequently and evaporate.Below this sample is denoted as sample D.
Embodiment 2 (comparative example)
This embodiment illustrates the following fact: for the conversion of oxygenate, the active catalyzer not necessarily good mutually of phosphatization.The result (sequentially) of step given in claims with and the blended not just simple diluting effect of binding agent.
By 25g sample B (comprising 5 % by weight phosphorus) extraly at 400 DEG C of dry 3h, and with distilled water at 80 DEG C of washing 2h, filter (P=3.4 % by weight, Al=2.7 % by weight) in room temperature subsequently.By the solid obtained by balancing at 600 DEG C of decatize 2h.
In fixed bed, downflow system stainless steel reactor, above use substantially pure methanol feeding at T at 2g catalyzer (35-45 order particle) in=550 DEG C and at the pressure of 0.5 bar gauge pressure and WHSV=1.6h -1under carry out catalyst test.Before catalysis runs (run), by the N of all catalyzer in flowing 2(5Nl/h) temperature of reaction is heated in.Product analysis is carried out online by the gas-chromatography being equipped with capillary column.In table 1, the catalytic performance of catalyzer to provide in carbon, with dry weight basis without on the basis of coke.
Table 1
MeOH is to the conversion of HC 6.64
C1 6.28
DME, in CH2 55.00
CH3OH, in CH2 38.36
Ethene 0.11
Propylene 0.11
C4 alkene 0.10
C5 alkene 0.02
Embodiment 3 (embodiment)
By 320g sample B and 400g particular adhesive (P=16.7 % by weight, Si=14.5, Mg=0.19, Al=0.018 % by weight, K=230ppm, Na=230ppm, Ca=20.3 % by weight), 165ml H 2o, 235ml comprise 34 % by weight SiO 2low sodium silicon dioxide gel and 2-3 % by weight to extrude additive blended.This mixture is stirred 30 minutes and extrudes.
Described particular adhesive be by by etc. the NH of quality 4h 2pO 4with xonotlite in an aqueous medium room temperature blended and produce (1g solid/4ml water).After stirring 60 minutes, the xonotlite of phosphatization is by filtering with liquid separation and being dried.Use the product of this drying as extruding component.
By extruded solid at drying at room temperature 24h, then dry 16h at elevated temperatures, washing subsequently at 600 DEG C of decatize 2h.Below this sample is denoted as E.
In fixed bed, downflow system stainless steel reactor, above use substantially pure methanol feeding at T at 2g catalyzer (35-45 order particle) in=550 DEG C and at 0.5 bar gauge pressure and WHSV=1.6h -1under carry out catalyst test.Before catalysis runs, by the N of all catalyzer in flowing 2(5Nl/h) temperature of reaction is heated in.Product analysis is carried out online by the gas-chromatography being equipped with capillary column.In table 1, the catalytic performance of catalyzer to provide in carbon, with dry weight basis without on the basis of coke.Described result provides for the average catalyst performance at 8 hours run durations.
Table 2
Embodiment 4 (comparative example, extrudes, 40 % by weight zeolites in catalyzer)
By 356g sample Awith 338.7g Nyacol (40 % by weight SiO 2colloidal sol), 311.3g pyrolytic silicon dioxide (FK500), 480ml H 2o with 2-3% extrudes together with additive and extrudes.By extruded solid at drying at room temperature 24h, then at 110 DEG C of dry 16h, subsequently at 500 DEG C of calcining 10h.Final sample comprises 40 % by weight zeolites and 60 % by weight SiO 2binding agent.The sample experience making this extrude and 0.5MNH 4cl ion-exchange 18h under reflux conditions, washes with water subsequently, at 110 DEG C of dry 16h and at 450 DEG C of calcining 6h.By this through shaping and through exchanging sample 3.1M H 3pO 4under reflux conditions process 4h (1g/4.2ml), cool subsequently, filter and at 110 DEG C of dry 16h.
By the sample of this phosphatization at room temperature with 0.1M calcium acetate solution washing 2h (1g/4.2ml).Then by this sample through washing at 110 DEG C of dry 16h, and at 600 DEG C at 100 % by weight H 2decatize 2h in O.
Embodiment 5 (comparative example, extrudes, in the catalyst 40 % by weight zeolites)
Sample from embodiment 4 is at room temperature washed once with 0.1M calcium acetate solution again, washing 2h (1g/4.2ml).Then by through washing sample at 110 DEG C of dry 16h and at 600 DEG C at 100 % by weight H 2decatize 2h in O.
Embodiment 4 and 5 illustrates when first sample experiences and the contacting of binding agent, the scheme subsequently during phosphatization.
Embodiment 6 (embodiment, extrudes, 40 % by weight zeolites in catalyzer)
By 4g sample Bat room temperature with 0.1M calcium acetate solution washing 2h (1g/4.2ml), to filter and at 110 DEG C of dry 16h.The sample of 4g drying and 6g particular adhesive and 2-3 % by weight are extruded additive with 40/60 zeolite/binder than together with extrude.Described binding agent is obtained by following: by 40g xonotlite and 10g aluminum oxide (Condea ~ 75 % by weight Al 2o 3), 50g (NH 4) H 2pO 4and 50mlH 2o is blended at 60 DEG C, subsequent filtration at 110 DEG C of dry 16h.Sodium content in this particular adhesive is 200ppm.
By extruded solid at 110 DEG C of dry 16h, subsequently at 600 DEG C of calcining 10h.
The sample that this embodiment shows pre-phosphatization by extruding together with low sodium binding agent for the manufacture of the catalyzer prepared.
Embodiment 7 (embodiment, spraying dry)
Make 356g sample A experienceswith 288g 85 % by weight H 3pO 4+ 972ml H 2o contact 4h under reflux conditions.Then, mixture is cooled to room temperature, and adds 336g low sodium alumina colloidal sol (20 % by weight aluminum oxide).The solution obtained under agitation is kept 30 minutes, slowly adds NH subsequently 4oH is until the pH value of solution obtained is about 6.5.Then, by this mixture ageing (maturation) at least 1h, add 48g kaolin and the low sodium silicon dioxide gel of 720g (34 % by weight SiO subsequently 2, 200ppm Na).The final pH of slurry is about ~ 6.The slurry obtained under agitation is kept at least 30 minutes and spraying dry.Spray-dried samples with water is washed, is dried and calcines 2h at 700 DEG C.
Embodiment 8 (embodiment, spraying dry)
Make 150g sample Bthe aqueous solution comprising the xonotlite that 1.5g disperses with 630ml contacts, add subsequently 450g low sodium silicon dioxide gel (in water 34 % by weight SiO 2, 200ppm Na).Then, this solution is stirred 1 hour and spraying dry.At room temperature wash spray-dired solid with water 2h, subsequent filtration, at 110 DEG C of dry 16h and 700 DEG C of calcinings.
Embodiment 9 (embodiment, spraying dry)
Make 100g sample Cthe aqueous solution comprising the xonotlite that 1g disperses with 420ml contacts, add subsequently 300g low sodium silicon dioxide gel (in water 34 % by weight SiO 2, 200ppm Na).Then, this solution is stirred 1 hour and spraying dry.At room temperature wash spray-dired solid with water 2h, subsequent filtration, at 110 DEG C of dry 16h and 700 DEG C of calcinings.
Embodiment 10 (embodiment, spraying dry)
Make 100g sample Dthe aqueous solution comprising the xonotlite that 1g disperses with 420ml contacts, add subsequently 150g low sodium silicon dioxide gel (in water 34 % by weight SiO 2, 200ppm Na).Then, this solution is stirred 1 hour and spraying dry.At room temperature wash spray-dired solid with water 2h, subsequent filtration, at 110 DEG C of dry 16h and 700 DEG C of calcinings.
Embodiment 11 (embodiment, spraying dry)
Make 100g sample Awith 25g 85 % by weight H 3pO 4under reflux conditions contact 4 hours, cool subsequently, and add the aqueous solution of xonotlite that 120ml comprises 7g dispersion.The slurry obtained under agitation is kept about 1h, add subsequently 300g low sodium silicon dioxide gel (in water 34 % by weight SiO 2, 200ppm Na).Then, this solution is stirred 1 hour and spraying dry.Also at room temperature spray-dired solid is washed with water 2h, subsequent filtration at 200 DEG C of dry 16h, dry, and at 700 DEG C of calcining 2h.
Embodiment 12 (MTO performance)
In fixed bed, downflow system stainless steel reactor, above use substantially pure methanol feeding at T at 2g catalyzer (35-45 order particle) in=550 DEG C and at 0.5 bar gauge pressure and WHSV=1.6h -1under carry out catalyst test.Before catalysis runs, by the N of all catalyzer in flowing 2(5Nl/h) temperature of reaction is heated in.Product analysis is carried out online by the gas-chromatography being equipped with capillary column.In table 1, the catalytic performance of catalyzer to provide in carbon, with dry weight basis without on the basis of coke.Described result provides for the average catalyst performance at initial 4 hours run durations.
Table 3
This data declaration obtains higher productivity of propylene on catalyzer prepared in accordance with the present invention.

Claims (8)

1. methanol to olefins (MTO) technique, it comprises: manufacture the method comprising the catalyzer of phosphorus-modified zeolite, and described method comprises the following steps with this order,
A) be introduced into by phosphorus and comprise in the zeolite of at least one ten-ring in the structure, the amount being wherein introduced into the phosphorus in zeolite is 0.5-30 % by weight, is wherein zeolite structuredly selected from MFI,
B) step phosphorus-modified zeolite a) is mixed with at least one component being selected from one or more binding agents, alkaline earth salt, rare earth metal salt and clay,
B) * is by by step b) in the mixture spraying dry that obtains and manufacture catalyzer body by described mixture,
C) optional drying step or optional drying step and washing step subsequently,
D) calcining step,
D*) optional washing step and drying subsequently,
And it is light olefin that methanol to olefins (MTO) technique to be included in methanol conversion under the existence of obtained catalyzer.
2. technique according to claim 1, wherein step a) in be introduced into the phosphorus in zeolite amount be 0.5-9%.
3. according to the technique of any one of claim 1-2, its mesolite (or molecular sieve) comprise be less than 1000wppm sodium, be less than the potassium of 1000wppm and be less than the iron of 1000wppm.
4., according to the technique of any one of claim 1-2, its mesolite comprises the redox and noble element and Zn, Cr, Ti, Rh, Mn, Ni, V, Mo, Co, Cu, Cd, Pt, Pd, Ir, Ru, Re that are less than 100ppm.
5., according to the technique of any one of claim 1-2, wherein alkaline-earth metal and rare earth metal salt are Ca, Mg, Sr, Ce, La or its combination.
6., according to the technique of any one of claim 1-2, wherein the ratio of P-zeolite is the 15-90 % by weight of catalyzer.
7., according to the technique of any one of claim 1-2, wherein the concentration of alkaline earth salt and rare earth metal salt counts the 0.1-15 % by weight of catalyzer with metal (Me).
8. technique according to claim 7, wherein in catalyzer, the mol ratio of (Al+Me)/P is in the scope of 0.5-3, and wherein Me is alkaline earth or rare earth.
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